CN1079449A - Remove the method for sulfocompound in anhydrating - Google Patents
Remove the method for sulfocompound in anhydrating Download PDFInfo
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- CN1079449A CN1079449A CN93105847A CN93105847A CN1079449A CN 1079449 A CN1079449 A CN 1079449A CN 93105847 A CN93105847 A CN 93105847A CN 93105847 A CN93105847 A CN 93105847A CN 1079449 A CN1079449 A CN 1079449A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/343—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for digestion of grease, fat, oil
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The present invention relates to a kind of method of from the water of low organic content, removing sulfocompound, by the anaerobic reduction reaction sulfocompound is reduced to sulfide, then with sulfide partial oxidation generting element sulphur.Adopt the inventive method, can overcome common anaerobic reduction reaction increases expense because of the consumption of electron donor(ED) shortcoming.
Description
The present invention relates to a kind of method of removing the middle sulfocompound that anhydrates.
People are unacceptable often sulfocompound in the water, and concerning vitriol, sulphite and thiosulphate, it mainly accumulates in water drain, chemical rich water (eutrophication), the mud.In addition, in the water that has a large amount of sulfocompounds to exist, usually contain heavy metal,, therefore do not wish to contain in the water these heavy metals especially because of it has toxicity.In the washing water one class waste liquid of discharging in the flue gas processing device, sulfocompound wherein, particularly sulphite are a kind of compositions that is difficult to remove.In the flue gas that power station discharged flue gas and trash burning produce, can produce acidifying sulfurous gas (SO owing to exist
2), so can cause than serious environmental and pollute.As for the acidifying deleterious effect is well-known, and other relief liquors that contain sulfocompound also have the waste liquid that produces in printing, mining, papermaking, rubber, process hides and the viscose glue industry.
In a broad sense, two kinds of methods of removing sulfocompound are arranged, i.e. physico-chemical process and biological method.
The physical chemistry treatment process comprises the precipitator method, ion exchange method and membrane filtration method (electrodialysis and reverse osmosis).The shortcoming of these methods is expense height, and produces a large amount of waste liquids.Concerning flue gas is handled, generally adopt lime and ammonia to adsorb.At this moment, form a large amount of gypsum or ammonium sulfate, wherein a part should be utilized again.Yet, particularly for gypsum because the requirement of gypsum quality has been tending towards saturated in the market of strictness and demand gypsum more, make that the possibility of consequent gypsum application is very little.
For bioremediation, vitriol and sulphite and other sulfocompounds are reduced to sulfide in the anaerobic treatment step, then with this sulfide oxidation generting element sulphur.This process is a prior art, for example can be referring to International Patent Application WO 91/16269 and Europe patent application 451922.
The advantage of this method is, owing to the sulphur that generates can utilize again, so only produce a spot of waste liquid.Yet its shortcoming is, particularly when containing organism hardly in the waste liquid, and must be to wherein adding electron donor(ED), so that provide enough reducing equivalents for sulphate reducing bacteria (SRB).Most important electron donor(ED) is methyl alcohol, ethanol, glucose and other carbohydrates, organic acid, and as acetate, propionic acid, butyric acid and lactic acid, hydrogen and carbon monoxide.The use of electron donor(ED) has increased the expense of the biological treatment process for sulfur removal of waste water greatly.
Have been found that the organic compound that contains two above carbon atoms, degraded under anaerobic generates hydrogen and acetate.Hydrogen can be used as the electron donor(ED) in the reduction reactions such as vitriol and sulphite, still, under usual conditions, has 50% acetate to be converted into methane by methanogen (MPB) approximately.Under common anaerobic condition, there is 90% methyl alcohol to be converted into methane approximately.At this moment, owing to produced methane, must add extra electron donor(ED) (increase expense), what generate simultaneously contains H
2The gas of S must wash and burn in stove to remove this gas.
Have been found that when sulphur compound in the waste water low to organic content carries out anaerobic treatment that several different methods is arranged, itself or when using separately or being used in combination, owing to almost there is not methane to produce, so the consumption of electron donor(ED) significantly reduces.
Processing method of the present invention is:
A1), keep the concentration of vitriol in the anaerobism water outlet (effluent) to be at least 500mg/l;
A2), keep the concentration of sulphite in the anaerobism water outlet to be at least 100mg/l;
B), keep salt concn in the anaerobism medium, represent with the sodium ion equivalent, be at least about 6g/l;
C), keep the concentration of sulfide in the anaerobism water inlet to be at least 100mg/l;
D), in the anaerobic treatment medium, introduce inhibitor, this inhibitor to the toxicity of methanogen greater than to the incomplete oxidation sulphate reducing bacteria or contain the toxicity of the sulphate reducing bacteria oxygen compound of a carbon atom.
The compound of sulfur-bearing is reduced to sulfide, needs electron donor(ED) and exist, shown in following vitriol, sulphite and thiosulphate reaction equation.
When processing contains hardly or do not contain organic water, must add this type of electron donor(ED).According to employed method, for example can use following electron donor(ED): hydrogen, carbon monoxide and organic compound, as lipid acid, alcohols, carbohydrate, starch and organic waste, preferably use methyl alcohol, ethanol, glucose, polysaccharide, as sucrose, starch or Mierocrystalline cellulose, or carboxylic acid (as lipid acid).
Following reaction equation is for example understood the effect of ethanol as electron donor(ED).
If desired, can also be to wherein adding nitrogen, phosphoric acid salt and trace element as nutrient substance.
Use the inventive method, improved the efficient of electron donor(ED) greatly.
Step a) relates to sulfate concentration (a1).According to the present invention, the minimum concentration of vitriol is the concentration of the vitriol in the anaerobic reactor water outlet.For mixing reactor, this concentration is exactly the concentration (anaerobism medium) of vitriol in the reactor.The minimum concentration of vitriol is particularly suitable for the relatively low waste water of those organic compound contents in the anaerobism water outlet, that is, and and must be during processing to those waste water that wherein add organic compound (electron donor(ED)).Low organic content can be expressed as its chemical oxygen demand (COD) (COD) and be lower than 2 grams, preferably is lower than 1.5gO
2/ g vitriol.Can also be expressed as the dissolved organic carbon content and be lower than 600mg/g vitriol.The vitriol minimum concentration is under equilibrium conditions and/or most of, and for example more than 50%, even 75% above initial vitriol has been reduced to particularly suitable under the condition of sulfide.
Under reaction conditions, sulphite and thiosulphate can generate vitriol through disproportionation reaction, so also can adopt the equivalent concentration of sulphite or thiosulphate.The disproportionation reaction equation of sulphite and thiosulphate is as follows:
As can be known, the reduction factor that vitriol is converted into sulphite is 4/3 * 80/96=1.11 from aforesaid equation, and the reduction factor that vitriol is converted into thiosulphate is 1 * 112/96=1.16.Therefore, the concentration of 500mg/l vitriol reaches the concentration corresponding to the 580mg/l thiosulphate corresponding to the concentration of 550mg/l sulphite.Yet, have been found that the sulphite content that is lower than corresponding sulfate concentration can promote to reduce the reaction that generates sulfide effectively.Therefore, the sulphite minimum concentration is 100mg/l in the inventive method.
Preferably, sulfate concentration is not less than 900mg/l in the anaerobism water outlet.The upper limit of sulfate concentration fixes on the upper limit (seeing b) of salt concn basically, is 50g/l for its upper limit concentration of sodium sulfate.Further, in anaerobic reactor, the amount that vitriol is converted into sulfide preferably is not more than 3g/l, because high sulfide concentration is to the toxic effect of SRB.If there is not restricted condition (as restriction electron donor(ED) and nutrient substance) in the reactor, the concentration of vitriol should not be higher than 3g/l in the reactor water inlet.For thiosulphate, its used concentration can be identical with the concentration of vitriol.
The concentration of sulphite in the anaerobism water outlet (a2) preferably is at least 300mg/l, is more preferably and is at least 400mg/l.The upper limit of sulfite concentration is determined by the toxicity of sulphite itself.Preferably, sulfite concentration is no more than 2g/l.
Can adopt the concentration of diverse ways control vitriol (sulphite, thiosulphate).In circulating system, the major part of wherein purifying waste water is used for circulation.As in flue gas desulfurization course, can control the concentration of vitriol (sulphite) by adjusting reaction conditions.In this way, water for high concentration sulfate (or sulphite) content, sulphate content＞7g/l for example, most of water wherein is used for circulation, only emit sub-fraction water, add-on that the concentration of vitriol can be by adjusting electron donor(ED) in the water or limiting nutrient such as phosphatic concentration are controlled.In the water treatment system that does not almost have recirculated water, its quantity discharged is inlet amount no better than, for example, and for protosulfate concentration, in the processing as the water of 1-7g/l, the sulfate reduction system is carried out in two steps, the first step, the concentration that keeps aforementioned vitriol in second step, is carried out reduction reaction.
The anerobe (in this step sulfocompound being reduced to sulfide) that can use in the anaerobic treatment step according to the inventive method is in particular sulphur reduction bacterium and sulphate reducing bacteria (SRB), belong to (Desulfovibrio) as desulfurization vibrio, Desulfotomaculum (Desulfotomaculum), the desulfurization pseudomonas bacillus belongs to (Desulfomonas), desulfurization Sphaerophorus (Desulfobulbus), Desulfobacter (Desulfobacter), Desulfococcus (Desulfococcus), desulfurization nematode Pseudomonas (Desulfonema), desulfurization Sarcina (Deulfosarcina), desulfurization (no brood cell) Bacillaceae (Desulfobacterium) and desulfurization sigmoid colon Pseudomonas (Desulforomas).
Can SRB be classified by metabolism.Complete oxidation sulphate reducing bacteria (c-SRB) can be oxidized to CO with its organic substrate
2, and incomplete oxidation sulphate reducing bacteria (i-SRB) is oxidized to the further acetate of oxidation with organic substrate.The rate of propagation of i-SRB is greatly faster than the rate of propagation (about 5 times) of c-SRB.Usually, by the cultivation of different anaerobic species and/or in reactor spontaneous propagation, the sulphate reducing bacteria that can obtain to suit.
Some is different for the vitriol of this type of SRB and the optimal concentration of sulphite and aforesaid vitriol and sulphite optimal concentration, for i-SRB, sulfate concentration is preferably 0.5～3g/l, be preferably 1～2g/l especially, and sulfite concentration is preferably 0.5-2g/l, is preferably 0.9-1.5g/l(Fig. 1 especially).For c-SRB, sulfate concentration is preferably 0.4-5g/l, be preferably 1-2g/l especially, and sulfite concentration is preferably 0.3-1.5g/l, is preferably 0.4-1g/l(Fig. 2 especially).Attached Fig. 1 and 2 shows the formation activity (mg/l medium/sky) of sulfide in the medium, the i.e. function of i-SRB and c-SRB and vitriol () and sulphite (+) concentration respectively.
According to step b), the concentration of salt is preferably more than the 6gNa/l.If select for use ethanol as electron donor(ED) under heat-resisting condition, preferred na concn is about 7g/l, i.e. 6-8g/l.Under other conditions, salt concn is preferably and is at least 7g/l, and more preferably 10-25gNa/l is preferably 12-14gNa/l especially.Do not contain the salt of sodium for containing other ions, adopt its respective concentration, for example for potassium, its concentration is not less than 10g/l, is preferably to be at least 12g/l.Specific conductivity can replace salt concn as a parameter: be at least 24mS/cm but be no more than 85mS/cm; Specific conductivity is preferably 24-48mS/cm especially.
Have been found that the sulfide minimum concentration is that 100mg/l is favourable relatively concerning SRB in the anaerobism water inlet.Sulfide minimum concentration according to step c), for example, can be by during the anaerobic reactor entry into service, adding sulfide reaches the water outlet of partial reaction device is circulated in the reactor water inlet, so that sulfide concentration remains on the required sulfide concentration level.Sulfide concentration preferably is at least 100mg/l, is more preferably to be at least 150mg/l, especially preferably is at least 200mg/l, and sulfide concentration is higher than and does not in general have further effect on the 500mg/l.
As preferred additional index, anerobe microbial film thickness should keep below 0.5mm, makes medium produce powerful turbulent flow usually, as to injecting gas wherein, can make microbial film reach above-mentioned requirements.Also can control thickness by selecting solid support material, when using " fixedly film " or filter bed (filter bed), the solid support material specific surface is preferably 50-250m
2/ m
3; When using fluidized-bed or air supporting circle (air-lift loop), specific surface can be greatly, can be up to 3000m
2/ m
3Microbial film thickness is preferably less than 0.25mm, in order to obtain thinner microbial film, uses flocculation mud to be better than using granule sludge.
Further find, the pH value of anaerobism medium is remained on more than 7.5, more help the carrying out that reacts.
The anaerobic treatment process preferably, part-time is at least, carries out at elevated temperatures, particularly carries out under 40-100 ℃.Can be continuously or keep high temperature basically continuously, for example, when the energy that uses is very cheap, such as hot flue gas and/or warm washings.Particularly preferred temperature is 45-70 ℃, and preferred temperature is 50-55 ℃.Anaerobic process also can be carried out under the intensification of a section.For the temperature reaction process of a section, particularly preferred temperature is 60-80 ℃, hot stage can remain one hour or several hrs to several days, as a week.
Step d) is the use about inhibitor, especially for the inhibitor that suppresses methanogen, in the anaerobic treatment medium, introduce inhibitor, can reduce the consumption of electron donor(ED), this inhibitor to the toxic action of methanogen greater than to the incomplete oxidation sulphate reducing bacteria or contain the toxic action of the sulphate reducing bacteria oxygenated compound of a carbon atom.
Remove in the middle sulfocompound method of anhydrating according to the present invention, with bacterium water is carried out anaerobic treatment, bacterium generally includes the incomplete oxidation sulphate reducing bacteria, contains the sulphate reducing bacteria oxygenated compound of a carbon atom, and methanogen.Usually, when used matrix contained plural carbon atom, i-SRB secreted acetate, and this acetate can only be degraded by c-SRB.Therefore, when using inhibitor according to the inventive method, if add electron donor(ED) again, effect can be better so, because electron donor(ED) can not produce acetate by the metabolism of bacterium, preferably, the compound that uses carbon atoms not or only contain a carbon atom is as electron donor(ED), as, methane, methyl alcohol, formaldehyde, formic acid and carbon monoxide.
Have been found that the halogenide that contains a carbon atom is suitable as the inhibitor of implementing the use of the inventive method method, wherein preferably uses chloroform as inhibitor.
What can select is that monochloro methane, methylene dichloride, tetrachloromethane also can use by the halogenide that only contains a carbon atom.Under the anaerobic condition in implementing the inventive method, tetrachloromethane can be converted into chloroform and/or contain the methane compounds of 3 following chlorine atoms.Remove the chlorination beyond the region of objective existence, bromide and iodide also are the good restraining agent.
The usage quantity of inhibitor is 0.01-20mg in every liter of treatment media for example, is preferably 0.05-5mg, and when using chloroform as inhibitor, its concentration has optimum activity when 0.1g/l.
Step d) can be with additive method a), and b), c) in a step or a few step combines.
The inventive method can be handled various water, for example under water, and mining draining, trade effluent such as printer, metallurgical industry, tanning industry, rubber industry, viscose fibre industry, paper industry and polymer trade effluent, and the washing water of flue gas treatment plant.
The invention still further relates to the treatment process of sulfur-containing smoke gas, flue gas at first is washed the liquid washing, the washings of regenerating then, and the regeneration of washings can be adopted the inventive method.When smoke treatment, in a big rinse bath, remove the SO in the flue gas
2, be dissolved in SO in the washing water then
2Enter in the anaerobic reactor.Dissolved SO
2Mainly the form with sulphite and hydrosulphite exists.In anaerobic biological reactor, sulphite and hydrosulphite are converted into sulfide.
Then, the sulfide of generation oxidized generting element sulphur in another reactor.Elementary sulfur can be used as the starting material of various uses.
Oxidizing reaction is preferably carried out in second bio-reactor, and in second bio-reactor, the control oxygen feeding amount is not so that the main oxidation generting element of sulfide sulphur generates or only generate very a spot of vitriol.By keeping the active sludge in the reactor to be lower aq and to stop the short time, can imitate ground control section oxidizing reaction.Yet reaction is preferably carried out under anaerobic environment.Amount of oxygen can make things convenient for and promptly adjust to the requirement of pending water.
Method of the present invention can be applicable to the processing of multiple sulfocompound widely: at first, the inventive method is particularly suitable for removing mineral sulfates and inorganic sulfite.Secondly, method of the present invention also can be with other inorganic sulfocompounds, as thiosulphate, tetrathionate, hyposulfite, elementary sulfurs etc. are removed from water, can also be with sulfur-containing organic compound, as sulfonated alkane, dialkyl sulfide, dialkyl group disulfide, mercaptan, sulfone, sulfoxide, dithiocarbonic anhydride etc. are removed from water.
If carry out rear oxidation, product then obtained by the method for the present invention is an elementary sulfur, can easily it be separated from water, for example adopts sedimentation method, filter method, centrifugal separation method or flotation process, and the elementary sulfur that obtains can utilize again.
With sulfide oxidation bacterium sulfide oxidation under anaerobic environment, can adopt Netherlands patent applications 88.01009 described methods, this moment, used bacterium can be selected from colourless sulphur bacteria class, as sulfo-bacillus (Thiobacillus), sulphur Microspira (Thiomicrospira), sulfolobus genus (Sulfolobus) or the like.
Table A has been listed the influence of sulfate concentration to the ethanol consumption, and the seed activity mud that obtains from paper-making industrial waste water is housed in the reactor, and this active sludge adds ethanol then.
Table A
Sulfate concentration in sulfate reduction to the influence of ethanol consumption
Sulfate concentration (mg/l) mole ethanol/molar sulphur hydrochlorate
500 1.04
1400 0.65
Table B has listed in sulfate reduction, and salt concn is to the influence of methyl alcohol (electron donor(ED)) consumption, and used active sludge is the active sludge in the waste water, adds methyl alcohol (30 ℃, pH=7.5,5 hours residence time) in this active sludge subsequently.The result shows, improves the sulfide of every generation 1kg after the salt concn, and the usage quantity of methyl alcohol only is original 25%.The big value of theoretical amount is 0.75kgS
2-/ kg methyl alcohol.
Salt concn is to the influence of methanol consumption amount in the table B sulfate reduction
| Salt concn (g/Na +/l) | With respect to total flow, the consumption % of methyl alcohol in the reduction process of vitriol | The kg number of the sulfide that the methyl alcohol of consumption 1kg obtains |
| 0.2 12.5 | 11% 50% | 0.09 0.38 |
Table C shows the influence of salt concn to sulfate reduction, is equipped with in the reactor with under the close mesomeric state condition, and from acetate, the seed activity mud that propionic salt and butyrates mixture obtain.
Table C salt concn is (with Na
+Concentration is represented) to sulfate reduction and the influence of producing methane content
| Salt concn Na +(g/l) | The maximum reduction ratio (w.r.%) of vitriol | The highest production rate (w.r.%) of |
| 5 7.5 10 12.5 15 | 100 100 100 100 55 | 100 50 25 10 5 |
Table D shows the influence of microbial film thickness to sulfate reduction, is added with the seed activity mud that obtains from acetate and glucose mixture in the reactor.
Table D microbial film thickness is to the influence of sulfate reduction and product methane content
| Active sludge particle diameter (mm) | Sulfate reduction amount (g/gVSS 1My god) | Methane generation (g/gVSS. days) |
| ＞2 1-2 0.5-1 0.25-0.5 0.125-0.25 | ＜0.1 ＜0.1 0.12 0.2 0.3 | 0.5 0.6 0.55 0.45 0.3 |
VSS
1: volatile suspended solid is not present in that part of suspended substance in the ash behind the sintering.
Table E has concluded the restraining effect of several muriate inhibitor, and these inhibitor are to MPB, and the maximum inhibition of i-SRB and c-SRB is respectively 50 or 80%, and listed numerical value is corresponding inhibitor concentration (mg/l).
Table E
Inhibitor MPB i-SRB c-SRB
50％ 80％ 50％?80％ 50％ 80％
To chlorophenylmethyl mercaptan 210 375 29 232 46 84
To chlorophenylmethyl chlorine 14 27 7 16 2 14
Chloroform 0.90 1.48 8.0＞100 0.7 1.4
Chlorobenzene 350.6 470.7 85 620 52 176
1,2-dichlorobenzene 179.4 260.2 34 118 39 116
1 94.4 119.8 58 172 37 88
2-chlorophenol 410.2 515.7 105 345 78 197
2,4 dichloro phenol 79.9 104.3 22 51 10 54
3-chloro-5 first hydrogen base phenol 65.0 125.3 32 108 21 78
Table F shows sulfide in the water into to the influence of sulfide output, the concentration of sulfide is 400mg/l in the water inlet, the anaerobic treatment condition is 30 ℃, pH=7.5, sulfate concentration is 1500mg/l in the water inlet, and methanol concentration is 1250mg/l in the water inlet, and the residence time is 5 hours, after 60 days, the methanol consumption amount increases by 40% during with SRB.
Table F
| Sulfide concentration in the water inlet | Sulfide output | The sulfide kg number that every consumption 1kg methyl alcohol produces |
| 0 400mg/l | 110mg/l 140mg/l | 0.09 0.18 |
Table G shows the generation activity of interrupter method anaerobism sulfide, and reaction conditions is 30 ℃, pH=7.5, and sulfate concentration is 1500mg/l in the water inlet, and alcohol concn is 1250mg/l in the water inlet, and its activity is the function of water sulfide concentration into.
Table G
| Initial sulfide concentration (mg/l) | Maximum activity (mgS 2-/ 1/ day) |
| 0 128 324 753 2013 | 127 160 243 252 0 |
Table H shows in the water outlet sulfide to the influence of methanol consumption amount
Table H
| Sulfide concentration (mg/l) | The kg number of the sulfide that every consumption 1kg methyl alcohol produces |
| 0 80 180 400 800 | 0.05 0.09 0.16 0.20 0.20 |
In the flue gas treating processes, can in device as shown in Figure 3, use method of the present invention.According to Fig. 3, contain SO
2Flue gas enter in the rinse bath 2 through 1, in rinse bath, flue gas with through the 3 washings countercurrent flows that enter, the flue gas after the processing is discharged or is further handled through 4.The washings that contains sulphite enters in the anaerobic reactor 6 through 5.Electron donor(ED) as ethanol, also enters in the anaerobic reactor 6 through 7.The gas that generates in the reactor is mainly CO
2And a spot of H
2S enters gas treatment equipment through 8.The anaerobism effluent, sulfide concentration wherein remains between the 300mg/l-2g/l, enters anaerobism or part anaerobic reactor 10 through 9, and air feeds anaerobic reactors 10 through 11.Excess air is through 12 dischargings.The sulfur-bearing water outlet enters settling bowl 14 through 13, isolates sulphur here and discharges through 15.Water in the sulfur deposition pond is discharged through 16, and the recycling washing water of doing, and a part can emit through 17, and make up water if desired can provide through 18, can contain buffer reagent and nutrient substance in the make up water.
Claims (20)
1, remove the method for sulfocompound from water, wherein water carries out anaerobic treatment through sulphur reduction bacterium and/or sulphate reducing bacteria, adds electron donor(ED) simultaneously, it is characterized in that taking following one or more steps to reduce the consumption of electron donor(ED):
A1) sulfate concentration is at least 500mg/l in the water outlet of maintenance anaerobism;
A2) keep the concentration of sulphite in the anaerobism water outlet to be at least 100mg/1;
B) salt concn in the maintenance anaerobism medium is represented with the sodium ion equivalent, is at least 6g/l;
C) sulfide concentration is at least 100mg/l in the water inlet of maintenance anaerobism;
D) in the anaerobic treatment medium, introduce inhibitor, this inhibitor to the toxicity of methanogen greater than to the incomplete oxidation sulphate reducing bacteria or contain the toxicity of the sulphate reducing bacteria oxygenated compound of a carbon atom.
2, keep anerobe microbial film thickness less than 0.5mm according to the process of claim 1 wherein, preferably make medium produce powerful turbulent flow and make anerobe microbial film thickness less than 0.5mm.
3, according to the method for claim 1 or 2, wherein sulfate concentration remains on and is at least 900mg/l in the anaerobism water outlet, is preferably 1-3g/l especially.
4, according to the method for claim 2, wherein sulfite concentration remains 300mg/l at least in the anaerobism water outlet, is preferably 0.4-2g/l.
5, according to each method among the claim 1-3, wherein the electric conductivity of water is at least 24mS/cm.
6, according to each method among the claim 1-5, wherein the concentration of sulfide is 200-500mg/l in the water inlet.
7, each method among the claim 1-6, wherein the pH value of anaerobism medium is greater than 7.5.
8, each method among the claim 1-7, wherein methyl alcohol, ethanol, organic acid, glucose, starch or Mierocrystalline cellulose are used as electron donor(ED).
9, according to each method among the claim 1-7, wherein use inhibitor and electron donor(ED), used electron donor(ED) is for the compound of carbon atoms not or contain the compound of a carbon atom, as hydrogen, methane, methyl alcohol, formic acid or carbon monoxide.
10, according to the method for claim 9, wherein will contain the halogenide of a carbon atom, be preferably chloroform, as inhibitor.
11, according to each method among the claim 1-10, wherein the usage quantity of inhibitor is the 0.01-20mg/l medium, is preferably the 0.05-5mg/l medium.
12, according to each method among the claim 1-11, wherein said processing is to carry out part-time at least under 40-100 ℃ the condition in temperature.
13, according to each method among the claim 1-12, wherein anaerobic treatment is carried out in two steps, and keeping the concentration of vitriol in first treatment step is high density, reduces the concentration of vitriol in second treatment step.
14, according to each method among the claim 1-13, wherein the water cycle after the part anaerobic treatment is used.
15, according to each method among the claim 1-14, wherein from water, remove vitriol.
16, according to each method among the claim 1-14, wherein from water, remove sulphite.
17, according to each method among the claim 1-14, wherein from water, remove thiosulphate.
18, according to each method among the claim 1-17, wherein the sulfide of Sheng Chenging is oxidized to elementary sulfur basically, and the sulphur that generates is removed.
19, according to the method for claim 18, wherein under anaerobic environment, sulfide is with sulfide oxidation bacterium partial oxidation.
20, handle the method for sulfur-containing smoke gas, wherein wash flue gas, and with washings regeneration, it is characterized in that with each method among the claim 1-19, regeneration washings with washings.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9200927 | 1992-05-26 | ||
| NL9200927A NL9200927A (en) | 1992-05-26 | 1992-05-26 | METHOD FOR REMOVING SULFUR COMPOUNDS FROM WATER. |
| NL9201268 | 1992-07-07 | ||
| NL9201268A NL9201268A (en) | 1992-07-14 | 1992-07-14 | Method of removing sulphur compounds from water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1079449A true CN1079449A (en) | 1993-12-15 |
| CN1092152C CN1092152C (en) | 2002-10-09 |
Family
ID=26646973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93105847A Expired - Fee Related CN1092152C (en) | 1992-05-26 | 1993-05-26 | Nethod for removing sulphur compounds from water |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5518619A (en) |
| CN (1) | CN1092152C (en) |
| NO (1) | NO306816B1 (en) |
| RU (1) | RU2108982C1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425551C (en) * | 2006-09-29 | 2008-10-15 | 合肥工业大学 | Mining area acid water treating process in the source |
| CN103415475A (en) * | 2010-12-02 | 2013-11-27 | 香港科技大学 | Biological wastewater treatment and reuse by utilizing sulfur compounds as electron carrier to minimize sludge production |
| CN104105671A (en) * | 2012-03-13 | 2014-10-15 | 株式会社大赛璐 | Waste water treatment method |
| CN111542662A (en) * | 2017-12-29 | 2020-08-14 | 维美德技术有限公司 | Method and system for adjusting S/Na balance of pulp mill |
| CN111676176A (en) * | 2020-07-22 | 2020-09-18 | 中国科学院过程工程研究所 | Halophilic alkalophilic sulfur micro-spirillum, culture method thereof and application thereof in biological desulfurization |
| CN112358133A (en) * | 2020-11-11 | 2021-02-12 | 深圳盛亚环境技术有限公司 | Method for removing heavy metals in electroplating wastewater |
| CN115159464A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulfite with sulfur-carbon composite material |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0819756A1 (en) * | 1996-07-16 | 1998-01-21 | Biostar Development C.V. | Sulphur reducing bacterium and its use in biological desulphurisation processes |
| BR9710618A (en) * | 1996-07-29 | 1999-08-17 | Paques Bio Syst Bv | Process for the biological treatment of a spent caustic solution and for the biological treatment of an aqueous solution |
| US6852305B2 (en) * | 1998-11-16 | 2005-02-08 | Paques Bio Systems B.V. | Process for the production of hydrogen sulphide from elemental sulphur and use thereof in heavy metal recovery |
| DE10314893A1 (en) * | 2003-04-01 | 2004-11-04 | Cristallo Holdings Inc., Edmonton | Process for surface activation and / or surface decarburization of sulfur-crosslinked rubber particles |
| US20080190844A1 (en) * | 2007-02-13 | 2008-08-14 | Richard Alan Haase | Methods, processes and apparatus for biological purification of a gas, liquid or solid; and hydrocarbon fuel from said processes |
| DE102007054209A1 (en) * | 2007-11-12 | 2009-05-14 | Voith Patent Gmbh | Process for the recovery of chemicals from wastewater |
| US20130157334A1 (en) * | 2011-12-19 | 2013-06-20 | Shell Oil Company | Process for converting a lignocellulosic biomass |
| EP3409642A1 (en) * | 2017-06-01 | 2018-12-05 | Paqell B.V. | A process to convert bisulphide to elemental sulphur |
| CN115594321B (en) * | 2021-06-28 | 2024-05-03 | 中国石油化工股份有限公司 | Method for treating high-sulfate organic wastewater |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124501A (en) * | 1977-08-04 | 1978-11-07 | University Of Southern California | Purifying oil shale retort water |
| US4200523A (en) * | 1978-03-23 | 1980-04-29 | E. I. Du Pont De Nemours And Company | Process for removing sulfate ions from aqueous streams |
| SU835972A1 (en) * | 1979-07-24 | 1981-06-07 | Уфимский Нефтяной Институт | Method of biochemical purification of waste water from sulfates |
| JPS5919595A (en) * | 1982-07-23 | 1984-02-01 | Ebara Infilco Co Ltd | Treatment of dithonic acid-contg. waste water |
| NL8401767A (en) * | 1983-06-20 | 1985-01-16 | Duncan Lagnese & Ass Inc | PROCESS FOR THE BIOLOGICAL REDUCTION OF SULFUR OXIDES. |
| JPS6054792A (en) * | 1983-09-02 | 1985-03-29 | Hitachi Ltd | Controlling device of biological denitrification process |
| US4584271A (en) * | 1983-09-28 | 1986-04-22 | Joy Manufacturing Company | Bacterial regeneration apparatus and process |
| US4519912A (en) * | 1984-06-01 | 1985-05-28 | Kerr-Mcgee Corporation | Process for the removal of sulfate and metals from aqueous solutions |
| US4614588A (en) * | 1985-08-22 | 1986-09-30 | Dorr-Oliver Incorporated | Method for sulfide toxicity reduction |
| JPS62155996A (en) * | 1985-12-27 | 1987-07-10 | Fuji Electric Co Ltd | Device for controlling injection of organic carbon source in biological denitrification process |
| SE466198B (en) * | 1986-09-24 | 1992-01-13 | Ac Biotechnics Ab | PROCEDURES BEFORE TREATMENT OF WATER ON BIOLOGICAL ROADS TO PURPOSE DUTY OF SULFUR SOCIETIES FROM WATER |
| GB9000236D0 (en) * | 1990-01-05 | 1990-03-07 | Shell Int Research | Waste treatment |
| FR2659076A1 (en) * | 1990-03-02 | 1991-09-06 | Centre Nat Rech Scient | BIOLOGICAL PROCESS FOR DENITRIATING LIQUID MEDIA AND APPARATUS FOR IMPLEMENTING SAID METHOD |
| NL9000876A (en) * | 1990-04-12 | 1991-11-01 | Pacques Bv | METHOD FOR REMOVING SULFUR COMPOUNDS FROM WATER. |
| RO108674B1 (en) * | 1990-04-12 | 1994-07-29 | Pacques Bv | Waters treatment processes which contain sulphur compounds |
| NL9002661A (en) * | 1990-12-04 | 1992-07-01 | Pacques Bv | PROCESS FOR THE REMOVAL OF H2S FROM GAS. |
| NL9100587A (en) * | 1991-04-04 | 1992-11-02 | Pacques Bv | METHOD FOR REMOVING SULFUR COMPOUNDS FROM WATER. |
-
1993
- 1993-05-26 US US08/338,599 patent/US5518619A/en not_active Expired - Lifetime
- 1993-05-26 RU RU94046118A patent/RU2108982C1/en active
- 1993-05-26 CN CN93105847A patent/CN1092152C/en not_active Expired - Fee Related
-
1994
- 1994-11-22 NO NO944462A patent/NO306816B1/en unknown
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425551C (en) * | 2006-09-29 | 2008-10-15 | 合肥工业大学 | Mining area acid water treating process in the source |
| CN103415475A (en) * | 2010-12-02 | 2013-11-27 | 香港科技大学 | Biological wastewater treatment and reuse by utilizing sulfur compounds as electron carrier to minimize sludge production |
| CN103415475B (en) * | 2010-12-02 | 2016-03-30 | 香港科技大学 | Using sulphur compound as electron carrier to realize the minimized biological sewage treatment of sludge yield and reuse |
| CN104105671A (en) * | 2012-03-13 | 2014-10-15 | 株式会社大赛璐 | Waste water treatment method |
| CN111542662A (en) * | 2017-12-29 | 2020-08-14 | 维美德技术有限公司 | Method and system for adjusting S/Na balance of pulp mill |
| US11619000B2 (en) | 2017-12-29 | 2023-04-04 | Valmet Technologies Oy | Method and a system for adjusting S/Na-balance of a pulp mill |
| US11634864B2 (en) | 2017-12-29 | 2023-04-25 | Valmet Technologies Oy | Method and a system for adjusting S/Na-balance of a pulp mill |
| CN111676176A (en) * | 2020-07-22 | 2020-09-18 | 中国科学院过程工程研究所 | Halophilic alkalophilic sulfur micro-spirillum, culture method thereof and application thereof in biological desulfurization |
| CN112358133A (en) * | 2020-11-11 | 2021-02-12 | 深圳盛亚环境技术有限公司 | Method for removing heavy metals in electroplating wastewater |
| CN115159464A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulfite with sulfur-carbon composite material |
| CN115159464B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulphite with sulfur-carbon composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| NO944462L (en) | 1994-11-25 |
| US5518619A (en) | 1996-05-21 |
| CN1092152C (en) | 2002-10-09 |
| RU94046118A (en) | 1996-09-20 |
| RU2108982C1 (en) | 1998-04-20 |
| NO306816B1 (en) | 1999-12-27 |
| NO944462D0 (en) | 1994-11-22 |
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